There's no excuse for rudeness so I think you have a legitimate complaint to Aegean on that front. I recommend sending them a note about your experience on the attitude of the cabin crew.
However, I don't think you have a leg to stand on on the safety front. While there are base regulations that all airlines have to comply with, many airlines go above and beyond the bare minimum. For example, British Airways announces before landing that all personal headphones must be removed for take-off/landing, but the BA ones for the IFE can be used since any announcements override the IFE content.
Aegean may very well have a policy that headphones must be out/off of the ear for take-off and landing. A quick check of images of their safety card seems to confirm this. In that case, the flight attendant was correct to ask you to remove them regardless of whether or not they were attached to a device.
If you complain to Aegean about the rudeness, I would ask them to clarify their headphone policy, but leave out the accusations about the crew not being safe and not knowing how to evacuate an aircraft. That is a very strong accusation and one for which you have no basis.
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